EP0127842A1 - Diphenol monoesters of carboxylic acids, process for their preparation, their use in the preparation of polyester carbonates, polyester carbonates obtained according to the invention and flame-retardant moulding compounds containing these polyester carbonates - Google Patents

Abstract

The present invention relates to diphenol monoesters of carboxylic acids, a process for their preparation, their use in the production of polyester carbonates, the polyester carbonates obtainable according to the invention and flame-retardant molding compositions containing these polyester carbonates.

Description

The present invention relates to a process for the preparation of diphenol monoesters of carboxylic acids, which is characterized in that carboxylic acids are reacted with high molecular weight polycarbonates using catalysts at temperatures between 150 ° C. and 350 ° _C. with elimination of CO ₂ , the Preparation of the diphenol monoesters, one diphenol polycarbonate equivalent is used per carboxylic acid group of the carboxylic acid used.

The reaction is based on the example of terephthalic acid and bisphenol A polycarbonate as follows:

Gegenstand der vorliegenden Erfindung sind außerdem Diphenolmonoester von Carbonsäuren, insbesondere von Monocarbonsäuren, Dicarbonsäuren, Tricarbonsäuren und Tetracarbonsäuren, also Monocarbonsäure-(diphenol)-monoester, Dicarbonsäure-bis-(diphenol)-monoester, Tricarbonsäure- tris-(diphenol)-monoester und Tetracarbonsäure-tetrakis-(diphenol)-monoester.

The present invention also relates to diphenol monoesters of carboxylic acids, in particular monocarboxylic acids, dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids, that is to say monocarboxylic acid (diphenol) monoesters, dicarboxylic acid bis (diphenol) monoesters, tricarboxylic acid tris (diphenol) monoesters and tetracarboxylic acid tetrakis (diphenol) monoesters.

Another object of the present invention is the use of the diphenol monoesters according to the invention for the production of polyester carbonates by the phase interface process or by the pyridine process.

The present invention further relates to the polyester carbonates obtainable by the process according to the invention and to flame-retardant molding compositions containing the polyester carbonates obtainable according to the invention.

According to US Pat. No. 4,129,594, aromatic dicarboxylic acid chlorides are produced which are used to produce aromatic oligomeric and polymeric bisphenol esters are used, · including, for example, the case of the simplest terephthalic acid bis-bisphenol A ester. The polyesters can be further converted to polyester carbonates by reaction with COCI ₂ . Isolation of the special bis-bisphenol A esters is not possible with this production method; rather, a mixture of bisphenol esters with the most varied degree of polymerization is obtained, with the result that the polyester polycarbonates obtained from these mixtures with COCl ₂ do not have a targeted segment structure .

The same applies to DE-OS 3 026 937.

Another synthetic route for polyester carbonates is based on the use of finished polycarbonate (see for example US Pat. No. 3,998,908, GB Pat. No. 954,500 and GB Pat. No. 898,775). In this melting process, the polycarbonates can be partially degraded (US Pat. No. 3,988,908) while they are reacted with the end groups of the polyesters. However, the complete degradation of the polycarbonates with reaction of the COOH groups of the polyesters is neither intended nor should it take place defacto (see, for example, US Pat. No. 3,998,908, column 4, lines 47-54 and column 2, lines 56-61 and Column 6, lines 8-46).

When producing branched polycarbonates, branching agents containing carboxylic acid are also used builds (see GB-PS 1 159 924, US-PS 3 816 373 and US-PS 4 001 184). However, no monomeric ester trisphenols or ester tetraphenols etc. are obtained here either.

According to DE-PS 2 254 918 (Le A 14 711), phenolic OH groups-containing orthoesters are prepared and used as branching agents for thermoplastic polycarbonates. The orthoesters are produced by transesterification of orthoacrylic esters with diphenols, that is to say by a method other than that of the present invention.

According to DE-OS 2 714 544, bisphenol A terephthalate carbonate copolymers and their preparation from bisphenol A, terephthaloyl chloride, phenols and phosgene are described. In our opinion, however, the polyester carbonates of the regular structure according to the present invention are not obtained by the process of this reference.

According to EU-PS 2218 (Le A 18 544) aromatic polyesters are produced in the presence of aromatic polycarbonates by a transesterification process with the use of bisphenols and diaryl esters of aromatic dicarboxylic acids. This method also does not provide the polyester carbonates of the present invention with the regular structure.

DE-OS 26 36 783 (Le A 16 689) and DE-OS 27 02 626 (Le A 17 356) describe the direct installation of carbon acids from a certain molecular weight together with diphenols and phosgene according to the interfacial process for the production of polyester carbonates. Again, the polyester carbonates of the present invention are not expected to be obtained with the regular structure.

wobei HO-Z-OH ein estergruppenfreies Diphenol ist.Bisphenol polycarbonate equivalent in the sense of the present invention is the structural unit of the following formula

where HO-Z-OH is a diphenol free of ester groups.

Catalysts suitable according to the invention for the preparation of the ester diphenols are, for example, 5-membered, heterocyclic compounds such as imidazole, pyrazole, indazole, 1,2,3-triazole, 1,2,4-triazole, benzimidazole, benzotriazole, 3-amino-1,2 , 4-triazole, 3-amino-1,2,4-triazole-carboxylic acid (5), tetrazole, 5-amino-tetrazole and amidines or salts of tertiary organic amines, tri- and tetralkylammonium hydroxides or alkali oxides, hydroxides, alcoholates , carbonates, sulfates or phosphonates.

The catalyst is used in amounts between 0.001 and 10% by weight, preferably 0.01 to 1% by weight, based on the total weight of the reaction mixture used.

The preferred reaction temperatures are between 180 ° C and 250 ° C.

The esterphenolates according to the invention are preferably produced in the absence of solvents for the reactants, that is to say in bulk. However, solvents for the carboxylic acids and / or for the polycarbonate can also be used, such as chlorobenzene, toluene, xylene, benzene or chlorinated hydrocarbons.

The reaction time for the preparation of the ester phenols is between 2 and 60 hours, depending on the reaction temperature and the type and amount of the catalyst.

The phenol formed during the reaction, which results from the chain limiters of the polycarbonates used, is removed by subsequent vacuum distillation.

worin "A" ein "p"-wertiger, gesättigter oder ungesättigter aliphatischer Rest mit vorzugsweise 1 bis 20 C-Atomen, ein cycloaliphatischer Rest mit vorzugsweise 5 bis 6 C-Atomen, ein araliphatischer Rest mit vorzugsweise 7-15 C-Atomen, oder ein die Heteroatome N, O und/oder S enthaltender heterocyclischer Rest mit 3 bis 12 C-Atomen und "p" eine ganze Zahl von 1 bis 4, besonders bevorzugt 2_-oder 3 ist. Im Falle von p = 2, kann -A- auch eine Einfachbindung sein.Carboxylic acids which can be used according to the invention are monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and any higher carboxylic acids. The carboxylic acids which can be used according to the invention can be aromatic, aliphatic, cycloaliphatic, araliphatic or heterocyclic carboxylic acids. They can be used alone or in a mixture with one another. Carboxylic acids which can be used according to the invention are, in particular, those of the formula (IV)

wherein "A" is a "p" -valent, saturated or unsaturated aliphatic radical with preferably 1 to 20 C atoms, a cycloaliphatic radical with preferably 5 to 6 C atoms, an araliphatic radical with preferably 7-15 C atoms, or a heterocyclic radical containing the heteroatoms N, O and / or S having 3 to 12 carbon atoms and "p" an integer from 1 to 4, particularly preferably 2 _- or 3. In the case of p = 2, -A- can also be a single bond.

worin X -O-, -S-, -SO₂-, -CO-, -CH₂- oder

ist.Aromatic radicals A in the sense of this definition are, for example, also those of the following structure

wherein X is -O-, -S-, -SO ₂ -, -CO-, -CH ₂ - or

is.

worin

oder

Carboxylic acids of the formula (IV) are, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, hydrogenated dimeric and hydrogenated trimeric fatty acids (from, for example, oleic acid or tall oil acid), fumaric acid, maleic acid, Hexahydroterephthalic acid, phthalic acid, isophthalic acid, terephthalate acid, benzene-1,3,5-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, naphthalene-1,5-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, diphenyl sulfone-4,4-dicarboxylic acid ^1-, butane tetracarboxylic acid, ethylene tetracarboxylic acid, pyromellitic acid, benzene-1,2,3,4-tetracarboxylic acid, benzene-1,2,3,5-tetracarboxylic acid, as well as compounds of the following formulas

wherein

or

worin "A" einer der für Formel (IV) genannten aromatischen Reste ist sowie "s" und "t" unabhängig voneinander eine ganze Zahl von 1 bis 3, vorzugsweise 1 oder 2 sind.Carboxylic acids which can be used according to the invention are in particular also carboxylic acids containing phenolic OH groups, in particular those of the formula (V)

wherein "A" is one of the aromatic radicals mentioned for formula (IV) and "s" and "t" are independently an integer from 1 to 3, preferably 1 or 2.

Phenolic OH-containing carboxylic acids of the formula (V) are, for example, 2-, 3-, 4-hydroxybenzoic acid, (α-hydroxybenzene) acetic acid, hydroxynaphthalene carboxylic acids, hydroxydiphenyl acetic acid, hydroxyanthracenecarboxylic acids, 2,4-dihydroxybenzoic acid, 3,5- Dihydroxybenzoic acid, 3,5-dihydroxy-2-naphthalenecarboxylic acid, 4,4'-dihydroxy- (1,1'-biphenyl) -2-carboxylic acid, 4,4'-bis- (4-hydroxyphenyl) pentanoic acid, 3 , 4,5 _T rihydroxybenzoesäure, 4-hydroxy-1,3-benzenedicarboxylic acid, 4-hydroxy-1,2-benzenedicarboxylic acid, 4,6-dihydroxy-1,3-benzenedicarboxylic acid, 2,5-dihydroxy-1, 4-benzenedicarboxylic acid and 3,3'-methylenebis (6-hydroxy) -5-methylbenzoic acid.

oder der Formel (VII)

worin _R ein zweiwertiger aromatischer Rest mit C₆-C₁₄, ein araliphatischer Rest mit C₇-C₂₀, ein aliphatischer Rest mit C₂-C₂₀ oder ein cycloaliphatischer Rest mit C_S-C₆ ist, der aromatische (C₆-C₁₂), cycloaliphatische (C₄-C₁₂) oder heterocyclische (C₃-C₁₂) Ringe enthalten kann und/oder Ether-, Keto-, Carbonsäureester- oder Sulfonbrücken enthalten kann und der gegebenenfalls durch Halogen, Nitro- oder Alkoxygruppen mit C₁-C₂₀-Alkylresten substituiert sein kann. Der Index n_a steht für eine ganze Zahl von 1-20, die Indices n_b und n_c können gleich oder verschieden sein und bedeuten eine ganze Zahl von 0-20.Dicarboxylic acids which can be used according to the invention are also carboxyl-containing esters of the formula (VI)

or of the formula (VII)

wherein _{R is} a divalent aromatic radical with C ₆ -C ₁₄ , an araliphatic radical with C ₇ -C ₂₀ , an aliphatic radical with C ₂ -C ₂₀ or a cycloaliphatic radical with C _S -C ₆ , the aromatic (C ₆ -C ₁₂ ), cycloaliphatic (C ₄ -C ₁₂ ) or heterocyclic (C ₃ -C ₁₂ ) rings can contain and / or ether, keto, carboxylic acid ester or sulfone bridges and which may be substituted by halogen, nitro or alkoxy groups with C ₁ -C ₂₀ alkyl radicals can be substituted. The index n _a stands for an integer from 1-20, the indices n _b and n _c can be the same or different and mean an integer from 0-20.

Possible examples of (R) are:

Monocarboxylic acids of the formula (IV) which can be used according to the invention are butyric acid, isobutyric acid, pentanoic acid, 2- and 3-methylpentanoic acids, 2,2-dimethylpropanoic acid, 2-ethylbutanoic acid, 2-ethylhexanoic acid, coconut fatty acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid and stearic acid, cycloacid and 3-cyclohexene-1-carboxylic acid, benzoic acid, methyl-benzoic acid, phenylacetic acid, 4-methylphenylacetic acid, dimethylbenzoic acid, 3-phenyl-2-propenoic acid, 1-naphthalene carboxylic acid and 1,1-biphenyl-4-carboxylic acid.

bestehen, wobei HO-Z-OH ein estergruppenfreies Diphenol ist und wobei -Z- ein estergruppenfreier aromatischer Rest mit vorzugsweise 6 bis 30 C-Atomen ist. Die geeigneten Polycarbonate können sowohl ohne oder mit Kettenabbrechern hergestellt sein.High molecular weight polycarbonates which are suitable according to the invention are in principle all the molecular weights Mw (weight average) between 10,000 and 200,000 (measured by the viscosity in CH ₂ C1 ₂ at 25 ° C. and a concentration of 0.5% by weight or by the light scattering method) and from structural units of the form

exist, where HO-Z-OH is an ester group-free diphenol and wherein -Z- is an ester group-free aromatic radical with preferably 6 to 30 carbon atoms. The suitable polycarbonates can be made either with or without chain terminators.

worin

• Q eine Einfachbindung, -CH₂-, CH₃-C-CH₃,
  
  -o-,
  
  -S- oder -S0₂- bedeutet und R₁ bis R₄ gleich oder verschieden sind und H, Halogen wie Chlor oder Brom, oder CH₃ bedeuten.

Suitable diphenols HO-Z-OH are in particular those of the formula (VIII)

wherein

• Q is a single bond, -CH ₂ -, CH ₃ -C-CH ₃ ,
  
  -O-,
  
  -S- or -S0 ₂ - means and R ₁ to R _{4 are the} same or different and are H, halogen such as chlorine or bromine, or CH ₃ .

• Dihydroxydiphenyle,
• Bis-(hydroxyphenyl)-alkane,
• Bis-(hydroxyphenyl)-cycloalkane,
• Bis-(hydroxyphenyl)-sulfide,
• Bis-(hydroxyphenyl)-ether,
• Bis-(hydroxyphenyl)-ketone,
• Bis-(hydroxyphenyl)-sulfoxide,
• Bis-(hydroxyphenyl)-sulfone und α, α '-Bis-(hydroxyphenyl)-diisopropylbenzol sowie deren kernalkylierte und kernhalogenierte Verbindungen. Diese und weitere geeignete Diphenole sind beispielsweise in den US-Patentschriften 3 028 365, 3 275 601, 3 148 172, 3 062 781 und 2 999 846, in den deutschen Offenlegungsschriften 1 570 703, 2 063 050, 2 063 052, der französischen Patentschrift 1 561 518 und in der Monographie "H.Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York, 1964" beschrieben.

Suitable diphenols HO-Z-OH are for example

• Dihydroxydiphenyls,
• Bis (hydroxyphenyl) alkanes,
• Bis (hydroxyphenyl) cycloalkanes,
• Bis (hydroxyphenyl) sulfides,
• Bis (hydroxyphenyl) ether,
• Bis (hydroxyphenyl) ketones,
• Bis (hydroxyphenyl) sulfoxides,
• Bis- (hydroxyphenyl) sulfones and α, α'-bis (hydroxyphenyl) diisopropylbenzene and their alkylated and halogenated compounds. These and other suitable diphenols are described, for example, in US Pat. Nos. 3,028,365, 3,275,601, 3,148,172, 3,062,781 and 2,999,846, in German Offenlegungsschriften 1,570,703, 2,063,050, 2,063,052, French Patent 1,561,518 and described in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York, 1964".

• 4,4'-Dihydroxy-diphenyl, 2,2-Bis-(4-hydroxyphenyl)-propan, Bis-(4-hydroxyphenyl)-methan, 2,4-Bis-(4-hydroxyphenyl)-2-methylbutan, α,α-Bis-(4-hydroxyphenyl)-p-düsopropyl- benzol, 2,2-Bis-(3-chlor-4-hydroxyphenyl)-propan, Bis-(hydroxyphenyl)-sulfid und 2,2-Bis-(3,5-dimethyl-4-hydroxyphenyl)-propan.

Suitable diphenols are, for example:

• 4,4'-dihydroxy-diphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, α , α-bis (4-hydroxyphenyl) p-diisopropyl benzene, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, bis (hydroxyphenyl) sulfide and 2,2-bis ( 3,5-dimethyl-4-hydroxyphenyl) propane.

The most important polycarbonates for the process according to the invention are homopolycarbonates and copolycarbonates with between 10,000 and 200,000, which consist of 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis - (4-hydroxyphenyl) cyclohexane, 4,4-dihydroxydiphenyl, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4- hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) thioether and 2,2-bis (3,5-dibromophenyl) propane Use of phenols or alkylphenols as chain terminators.

According to the invention, one or more polycarbonates can be used.

worin "A" und "p" die für Formel (IV) genannte Bedeutung haben und -Z- der bereits definierte estergruppenfreie aromatische Rest mit vorzugsweise 6 bis 30 C-Atomen ist.The diphenol monoesters of carboxylic acids according to the invention are in particular those of the formula (IVa)

in which "A" and "p" have the meaning given for formula (IV) and -Z- is the aromatic radical which has already been defined and is preferably 6 to 30 carbon atoms and is free of ester groups.

worin "A", "s" und "t" die für Formel (V) genannte Bedeutung haben und -Z- die vorstehend für (IVa) genannte Bedeutung hat.The diphenol monoesters of carboxylic acids according to the invention are in particular also those of the formula (Va)

wherein "A", "s" and "t" have the meaning given for formula (V) and -Z- has the meaning given above for (IVa).

worin R, n_a, n_b und n_c die für die Carbonsäuren der Formeln (VI) und (VII) genannte Bedeutung haben und -Z- die vorstehend für (IVa) genannte Bedeutung hat.Dicarboxylic acid bis (diphenol) monoesters according to the invention are also those of the formulas (VIa) and (VIIa)

wherein R, n _a , n _b and n _{c have} the meaning given for the carboxylic acids of the formulas (VI) and (VII) and -Z- has the meaning given above for (IVa).

Dicarboxylic acid bis (diphenol) monoesters according to the invention are, for example, those of the following formulas (IVa ₁ ) to (IVa ₈ ), in which "A" has the meaning given for formula (IV).

Examples of diphenol monoesters of carboxylic acids of the formulas (IVa), (Va), (VIa) and (VIIa) are the following

Examples of diphenol monoesters of monocarboxylic acids of formula (IVa) in which p = 1 are as follows

The diphenol monoesters of carboxylic acids according to the invention can be used to produce polyester carbonates by the two-phase interface process known for polycarbonate synthesis, polyester carbonates of a particular desired and regular structure being obtained by the choice of defined amounts of defined starting materials.

If diphenol monoesters with two phenolic OH groups are concerned, ie dicarboxylic acid bis (diphenol) monoesters or lionohydroxyaryl monocarboxylic acid (diphenol) monoesters, they can be used as linear chain building blocks; Diphenol monoesters of monocarboxylic acids with a phenolic OH group serve as Chain limiters and diphenol monoesters of carboxylic acids with a total of three or more than three phenolic O _H groups serve as chain branching agents.

The present invention thus relates to the production of polyester carbonates from diphenols, phosgene, optionally chain terminators in the known amounts and optionally branching agents in the known amounts by the known two-phase interface process at pH values between 9 and 14, at temperatures between 0 ° C and 80 ° C, preferably 15 ° C and 40 ° C using the usual organic solvents and using the usual polycondensation catalysts, which is characterized in that the diphenols according to the invention are diphenol monoesters of carboxylic acids with two phenolic OH groups, optionally in combination with the ester group-free diphenols HO-Z-OH, in which -Z- is an aromatic-divalent radical free from ester groups, optionally with the use of monocarboxylic acid (diphenol) monoesters with a phenolic OH group as chain terminator and optionally with the use of diphenol monoesters of carboxylic acids three or more than three phenolic OH groups are used as branching agents, the diphenol monoesters used in each case being dissolved beforehand by carboxylic acids in the organic phase of the two-phase mixture.

The present invention also relates to the polyester carbonates obtainable by this process according to the invention.

The molar ratio of diphenol monoesters with two phenolic OH groups to diphenols HO-Z-OH free of ester groups depends on the molecular weight of the diphenol esters used and is between 1: 0.01 and 1: 300, preferably between 1: 0.05 and 1: 150 .

In addition to or instead of the monocarboxylic acid (diphenol) monoesters with a phenolic OH group of the present invention, the customary monofunctional chain terminators such as phenol, alkylphenols or halophenols can be used; the amount of monofunctional chain terminator, based on the use of diphenol monoesters with two phenolic OH end groups and free diphenols, is between 0.1 and 20 mol%, preferably between 1 and 5 mol%.

In addition to or instead of the diphenol monoesters of carboxylic acids with three or more than three phenolic OH groups of the present invention, the customary three-functional or more than three-functional branching agents, in particular those with three or more than three phenolic OH groups, can be used.

The total amount of branching agents to be used in each case is between 0.05 and 2 mol%, based on moles of diphenols.

Some of the known branching agents are, for example, phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenol) -heptane, 1,3, S-tri- (4-hydroxyphenyl) -benzene, 1,1, 1-tri- (4-hydroxyphenyl) -ethane, tris- (4-hydroxyphenyl) -phenyl-methane, 2,2-bis- [4,4-bis- (4-hydroxyphenyl) -cyciohexyl] propane, tetra- (4-hydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane and 1,4-bis- [4,4 "-dihydroxytriphenyl-methyl] benzene.

Of the ester group-free diphenols HO-Z-OH to be used optionally for the production of the polyester carbonates according to the invention, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) are preferred propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are used. Any mixtures of these diphenols can also be used.

Suitable organic solvents for the two-phase interface process are those known for the thermoplastic polycarbonates, such as, for example, methylene chloride or chlorobenzene.

Suitable polycondensation catalysts for the two-phase interface process are, for example, the tertiary aliphatic amine catalysts known for polycarbonate synthesis, such as trimethylamine, triethylamine, n-tripropylamine, n-tributylamine or N-ethylpiperidine; if necessary, the known quaternary ammonium salts such as tetrabutylammonium bromide can also be used.

Solutions of LiOH, NaOH, KOH, Ca (OH) ₂ and / or Ba (OH) ₂ in water are suitable for the preparation of the aqueous alkaline phase.

The amount of phosgene per mole of diphenol monoester with two phenolic OH groups and ester group-free diphenol is between 1 and 3 moles, preferably between 1.1 and 2 moles.

The reaction times for the production of polyester carbonate are between 5 minutes and 90 minutes for the phosgenation and between 3 minutes and 3 hours for the polycondensation after the addition of catalyst.

The two-phase interface process can expediently be carried out with the use of 0.1 to 1% by weight, based on the total weight of difunctional reaction partners, of reducing alkaline substances such as sodium borohydride or sodium sulfite.

The organic solutions of the polyester carbonates obtained by the two-phase interface process according to the invention are separated off and purified in the manner known for thermoplastic polycarbonates.

The polyester carbonates produced are isolated from the organic solutions in a known manner, for example by evaporating the solution, an evaporation extruder being used in the final stage of evaporation.

Other types of insulation are the precipitation by adding non-solvents or the immediate pouring of the concentrated solutions into films.

The polyester carbonates of the present invention generally have relative solution viscosities from 1.18 to 2.0, in particular from 1.2 to 1.5 (measured in 0.5 g / 100 ml of solution in CH ₂ C1 ₂ at 25 ° C.) .

The polyester carbonates of the present invention are produced by extrusion as uniform granules and can be processed into moldings by injection molding. They are also suitable for the production of films and coatings.

The polyester carbonates of the present invention can be provided with a wide variety of additives, stabilizers, flame retardants and fillers in a known manner during or after their preparation, that is to say with antioxidants, UV stabilizers, mold release agents, organic halogen compounds, alkali metal sulfonates, glass fibers, glass balls, barium sulfate, TiO ₂ and other additives known for the thermoplastic polycarbonates.

The polyester carbonates of the present invention, in particular in combination with the known flame retardants, for example in combination with potassium perfluorobutanesulfonate and N-methyltetrachlorophthalimide, show improved flame resistance.

The present invention thus also relates to molding compositions comprising the polyester carbonates obtainable according to the invention, alkali metal salts of perfluoroalkanesulfonic acids or arylsulfonic acids in amounts of q05-2% by weight and optionally N-alkyltetrachlorophthalimides, polyhalodiphenyls, polyhalodiphenyl ethers or oligocarbonates of tetrahalobisphenol-A in amounts of , 3-5 wt .-%, based on the total weight of the molding compound.

The polyester carbonates of the present invention can be used wherever the thermoplastic, aromatic polycarbonates have hitherto been used, but a higher glass transition temperature is desired, ie in the range from 150 ° C. to 175 ° C.

• I. Herstellung von Diphenolmonoestern von Carbonsäuren
  • I.1 Herstellung von Terephthalsäure-bis-[2,2-bis-(4-hydroxyphenyl)-propan7-monoester.
    
    
    In einem Rührautoklaven werden 2490 g Terephthalsäure, 8010 g lineares Bisphenol-A-Polycarbonat (mit η rel: 1,28 und mit 89 g eingebautem Phenol als Kettenabbrecher) und 25 g Imidazol vorgelegt. Unter Rühren und N₂-Atmosphäre wird diese Mischung innerhalb 2 h auf 220°C erhitzt. Man läßt 8 h bei dieser Temperatur rühren, danach wird 4 h bei 250°C erhitzt. Während dieser Zeit werden 705 1 CO₂ abgespalten. Anschließend wird ein Vakuum von 1 Torr angelegt. Das glasartige, braun gefärbte Produkt hat folgende Kennzahlen:
    • SZ 0,9
    • OHZ 178 gefunden
    • OHZ 190 berechnet.
  • I.2 Herstellung von p-Hydroxybenzoesäure-[2,2-bis-(4-hydroxyphenyl)-propan/-monoester.
    
    
    In einem Rührautoklaven werden 2071,8 g p-Hydroxybenzoesäure, 4005 g eines Bisphenol-A-Polycarbonats (mit η rel: 1,28 und mit 44,5 g eingebautem Phenol als Kettenabbrecher) und 15 g Imidazol vorgelegt. Unter Rühren und N₂-Atmosphäre wird diese Mischung innerhalb 2 h auf 200°C erhitzt. Ab ca. 150°C tritt CO₂-Abspaltung ein. Man läßt die Reaktionsmischung noch 5 h bei dieser Temperatur rühren, bis ca. 330 1 C0₂ abgespalten sind und die Säurezahl ca. 1,5 beträgt. Anschließend wird ein Vakuum von 1 Torr angelegt. Das glasartige, leicht gefärbte, transparente Produkt hat folgende Kennzahlen:
    • SZ 1
    • OHZ 298 gefunden
    • OHZ 321 berechnet.
  • I.3 Herstellung von Adipinsäure-bis-[2,2-bis-(4-hydroxyphenyl)-propan]-monoester
    
    
    In einem Rührkolben werden 14,6 g Adipinsäure, 53,4 g Bisphenol-A-Polycarbonat (mit η rel: 1,28 und mit 0,59 g eingebautem Phenol als Kettenabbrecher)und 0,6 g Imidazol vorgelegt. Unter Rühren wird diese Mischung innerhalb 30 Minuten auf 200°C erhitzt. Nach ca. 2 h ist die CO₂-Abspaltung beendet. Danach wird 1 h ein Vakuum von 20 Torr angelegt. Das glasartige, braun gefärbte Produkt hat folgende Kennzahlen:
    • SZ 1
    • OHZ 190 gefunden
    • OHZ 197,6 berechnet.
  • 1.4 Herstellung des Bis-[2,2-bis-(4-hydroxyphenyl)-propan/-monoesters der hydrierten Dimerfettsäure.
    In einem Rührkolben werden 53,4 g Bisphenol-A-Polycarbonat, (mit t rel: 1,28 und mit 0,59 g eingebautem Phenol als Kettenabbrecher), 56 g hydrierte Dimerfettsäure Mn 560 (Empol 1010 der Unilever Emery) und 0,6 g Imidazol vorgelegt. Innerhalb 30 Minuten wird diese Mischung auf 200°C erhitzt. Nach 4 h ist die CO₂-Abspaltung beendet. Anschließend wird 1 h ein Vakuum von 20 Torr angelegt. Das bräunliche, harzartige Produkt besitzt folgende Kennzahlen:
    • SZ 0,5
    • OHZ 144 berechnet
    • OHZ 105 gefunden.
  • I.5 Herstellung von Sebacinsäure-bis-[2,2-bis-(4-hydroxyphenyl)-propan/-monoesters
    
    
    In einem Rührkolben werden 20,2 g Sebacinsäure, 53,4 g Bisphenol-A-Polycarbonat (mit η rel: 1,28 und mit 0,59 g eingebautem Phenol als Kettenabbrecher) und 0,6 g Imidazol vorgelegt. Unter Rühren wird diese Mischung innerhalb 30 Minuten auf 200°C erhitzt. Nach ca. 2 h ist die C0₂-Abspaltung beendet. Anschließend wird 1 h ein Vakuum von 20 Torr angelegt.
    Das bräunliche, leicht harzige Produkt besitzt folgende Kennzahlen:
    • SZ 0,5
    • OHZ 180 berechnet
    • OHZ 174 gefunden.
  • I.6 Herstellung des Bis-L2,2-bis-(4-hydroxyphenyl)-propan7-monoesters eines hydrierten Dimerfettsäurehexandiol-Polyesters.
    In einem Rührkolben werden 120,2 g eines COOHterminierten, hydrierten Dimerfettsäure-hexandiol-Polyesters (Mn = 1220; OH-Zahl = 92), 53,4 g Bisphenol-A-Polycarbonat, (mit η rel: 1,28, und mit 0,59 g eingebautem Phenolals Kettenabbrecner) und 0,6 g Imidazol vorgelegt. Unter Rühren wird diese Mischung innerhalb 30 Minuten auf 200°C erhitzt. Nach etwa 4 h ist die CO₂-AbsDaltunq beendet. Anschließend wird ein Vakuum von 20 Torr angelegt. Das bräunliche öl hat folgende Kennzahlen:
    • SZ 0,5
    • OHZ S2 berechnet
    • OHZ 85 gefunden.
  • 1.7 Herstellung eines Gemisches aus Terephthalsäure-bis-[2,2-bis-(4-hydroxyphenyl)-propan]-monoesters und Isophthalsäure-bis-[2,2-bis-(4-hydroxyphenyly- propan/-monoesters im Molverhältnis 1:1.
    
    
    In einem Rührkolben werden 1,245 kg Terephthalsäure, 1,245 kg Isophthalsäure, 8,010 kg Bisphenol-A-Polycarbonat, (mitt rel: 1,28 und mit 88,9 g eingebautem Phenol als Kettenabbrecher) und 7,5 g Imidazol vorgelegt. Unter Rühren und N2-Atmosphäre wird diese Mischung innerhalb 2 Stunden auf 220°C erhitzt. Ab ca. 150°C tritt langsam die CO₂-Abspaltung ein, die mit steigender Reaktionstemperatur stärker wird. Man läßt die Reaktionsmischung noch 11 h bei dieser Temperatur rühren, bis ca. 700 1 C0₂ abgespalten sind und die Säurezahl 0,6 beträgt. Zur weiteren Vervollständigung der Reaktion und Abtrennung von freiem Phenol aus dem Reaktionsgemisch wird ein Vakuum von ca. 1 Torr angelegt. Es werden innerhalb 1 h bei ca. 1 Torr 380 g Phenol abdestilliert. Das glasartige, leicht braun gefärbte, transparente Produkt hat folgende Kennzahlen:
    • SZ 0,5
    • OHZ 186-187 gefunden
    • OHZ 190 berechnet.
  • I.8 Herstellung eines Gemisches gemäß Beispiel I.7 aber im Molverhältnis 3:1.
    In einem Rührautoklaven werden 1245 g Terephthalsäure, 415 g Isophthalsäure, 5340,3 g Bisphenol-A-Polycarbonat, (mit η rel: 1,28 und mit 59,4 g eingebautem Phenol als Kettenabbrecher) und 15 g Imidazol vorgelegt. Unter Rühren und N₂-Atmosphäre wird diese Mischung innerhalb 2 h auf 200°C erhitzt. Ab ca. 150°C tritt langsam CO₂-Abspaltung ein. Die Reaktionsmischung wird noch 18 h bei dieser Temperatur gerührt, während gleichzeitig 470 1 C0₂ abgespalten werden und die Säurezahl gegen Ende der Reaktion 0,9 beträgt. Danach wird innerhalb 1 h ein Vakuum von 1 Torr angelegt. Das glasartige, leicht braun gefärbte, transparente und spröde Produkt hat folgende Kennzahlen:
    • SZ 0,6
    • OHZ 185-187 gefunden
    • OHZ 190 berechnet.
  • I.9 Herstellung eines Gemisches gemäß Beispiel I.7, aber im Molverhältnis 9:1.
    In einem Rührautoklaven werden 2241 g Terephthalsäure, 249 g Isophthalsäure, 8010 g Bisphenol-A-Polycarbonat, (mit η rel: 1,28 und mit 89 g eingebautem Phenol als Kettenabbrecher) und 25 g Imidazol vorgelegt. Unter Rühren und N₂-Atmosphäre wird diese Mischung innerhalb 2 h auf 220°C erhitzt. Die Reaktionsmischung wird noch 7 h bei dieser Temperatur gerührt, während gleichzeitig 702 1 C0₂ abgespalten werden und die Säurezahl 0,8 beträgt. Danach wird an das glasartige, spröde und später kristallin werdende Produkt innerhalb 1 h ein Vakuum von 1 Torr bei 250°C angelegt. Das erhaltene Produkt hat folgende Kennzahlen:
    • SZ 0,7
    • OHZ 184-185 gefunden
    • OHZ 190 berechnet.
• II. Herstellung von Polyestercarbonaten
  • II.1 Herstellung eines Polyester-Polycarbonats mit folgenden Struktureinheiten
    
    
    In einem Rührkessel werden 36 1 destilliertes Wasser, 1049 g 45 %ige Natronlauge und 61,2 g p-tert.-Butylphenol gelöst. Dazu wird eine Lösung aus 25,2 1 Methylenchlorid, 10,8 1 Chlorbenzol und 4,780 kg des Gemisches des Beispiels I.7 gegeben. Innerhalb 40 Minuten werden unter Rühren und Stickstoffatmosphäre 1,612 kg Phosgen unter Rühren bei pH 13 eingeleitet, während gleichzeitig zur Konstanthaltung von pH 13 1,5 kg 45 %ige Natronlauge zugetropft werden. Danach werden 11,26 ml N-Ethylpiperidin (1 Mol-%) zugegeben und es wird eine Stunde gerührt. Die organische Phase wird abgetrennt, nacheinander mit 2 %iger Phosphorsäure und schließlich mit dest. Wasser bis zur Elektrolytfreiheit gewaschen. Durch Abdestillieren des Methylenchlorid erhält man eine Chlorbenzollösung aus der das Polymer in einem Ausdampfextruder bei 310°C Extrudertemperatur isoliert wird. Die rel. Viskosität des Polyestercarbonats beträgt η rel = 1,265 (0,5 g in 100 ml CH₂ Cl₂) (Mechanische Eigenschaften siehe nachfolgende Tabelle).
  • II.2 Herstellung eines Polyestercarbonats aus 30 Gew.-% aromatischem Polyester und 70 Gew.-% Bisphenol-A-Polycarbonat
    In einem Rührkessel werden 2,185 kg Bisphenol A, 72,4 g p-tert.-Butylphenol, 36 1 destilliertes Wasser und 2,500 kg 45 %ige Natronlauge gelöst. Dazu wird eine Lösung aus 2,456 kg des Gemisches des Beispiels I.7, 10,8 1 Chlorbenzol und 25,2 1 Methylenchlorid gegeben. Unter Stickstoffatmosphäre werden in diese Reaktionsmischung bei pH 13 2,722 kg Phosgen bei 20-25°C eingeleitet, während gleichzeitig zur Konstanthaltung von pH 13 insgesamt 5,3 kg 45 %ige Natronlauge zugetropft werden.
    Danach werden 19 ml N-Ethylpiperidin (1 Mol-%) zugegeben und es wird 1 Stunde gerührt. Das Reaktionsprodukt wird wie in Beispiel II.1 aufgearbeitet.
    Das isolierte Polyesterpolycarbonat hat folgende Kennzahlen:
    η rel = 1,290
    ( echanische Eigenschaften siehe nachfolgende Tabelle).
  • II.3 Herstellung eines Polyestercarbonats aus 50 Mol-% aromatischem Polyester (75 Mol-% Terephthalsäure und 25 Mol-% Isophthalsäure) mit 50 Mol-% Bisphenol A-Polycarbonat
    In einem Rührkessel werden 1049 g 45 %ige NaOH, 61,2 g p-tert.-Butylphenol und 36 1 destilliertes Wasser gegeben. Dazu wird eine Lösung aus 4,780 kg des Gemisches des Beispiels 1.8, 10.8 1 Chlorbenzol und 25.2 1 Methylenchlorid gegeben. Innerhalb 40 Minuten werden unter Rühren und Stickstoffatmosphäre 1,612 kg Phosgen unter Zugabe von 1,5 kg NaOH 45 %ig eingeleitet. Die weitere Aufarbeitung erfolgt wie Beispiel II.1. Die relative Viskosität des Polyestercarbonats beträgt η rel = 1,277. Mechanische Eigenschaften siehe nachfolgende Tabelle.
  • II.4 Herstellung eines Polyestercarbonats aus 30 Gew.-% aromatischen Polyesters (90 Mol-% Terephthalsäure und 10 Mol-% Isophthalsäure) und 70 Gew.-% Bisphenol A-Polycarbonat In einem Rührkessel werden 2,185 kg Bisphenol A, 72,4 g p-tert.-Butylphenol, 36 1 destilliertes Wasser und 2,5 kg 45 %ige NaOH gelöst. Dazu wird eine Lösung aus 2,456 kg des Gemisches des Beispiels I.9, 10,8 1 Chlorbenzol und 25,2 1 Methylenchlorid gegeben. In diese Reaktionsmischung werden unter Rühren 2,722 kg Phosgen eingeleitet und wie in den Beispielen II.1 und II.2 aufgearbeitet. Das isolierte Polyester-Polycarbonat besitzt folgende Kennzahlen:
    η rel = 1,264
    Mechanische Eigenschaften siehe nachfolgende Tabelle.
  • _II.5 Herstellung eines Polyestercarbonats aus 1 Mol p-Hydroxybenzoesäure und 1 Mol Bisphenol A
    In einen Rührkessel werden 2,133 kg 45 %ige _Na-tronlauge, 179,9 g p-tert.-Butylphenol und 36 1 destilliertes Wasser gegeben. Dazu wird eine Lösung aus 4370 g des p-Hydroxybenzoesäure-Bisphenol-A-esters aus Beispiel I.2 gelöst in 25,2 1 Methylenchlorid und 10,8 g Chlorbenzol gegeben. Innerhalb 30 Min. werden unter Rühren und N₂-Atmosphäre 2,370 kg Phosgen bei pH 14 unter Zugabe von 5,2 kg 45 % NaOH eingeleitet. Anschließend werden 16,5 ml N-Ethylpiperidin zugegeben und danach noch 1 h gerührt. Die organische Phase wird wie in Beispiel II.1 aufgearbeitet. Die relative Viskosität des Polyestercarbonats beträgt M rel = 1,31. Das Produkt zeigt nach DTA-Analyse eine Einfriertemperatur Tg von 155°C.
    
    Die Eigenschaften der vorstehenden Tabelle wurden gemessen nach:
    • 1. Carbonat-Ester-Verhältnis
    • 2. Terephthals.-Isophthalsäure-Verhältnis
      • a) DIN 53455
      • b) DIN 53457
      • c) DIN 53453
      • d) DIN VST/B/50
• _III. In der nachfolgenden Tabelle II werden die Polyestercarbonate II.2, II.3 und II.4 mit einem konventionellen Polyestercarbonat verglichen. Das konventionelle Polyestercarbonat besteht aus einem Gemisch aus Terephthalsäure und Isophthalsäure mit einem Molverhältnis von 1:1 und Bisphenol A und wurde nach dem Phasengrenzflächenverfahren aus den Säurechloriden der Terephthalsäure und Isophthalsäure herstellt; es hat eine relative Lösungsviskosität η rel von 1,26. Es wurde abgemischt mit Bisphenol A-Polycarbonat (η rel: 1,28) mit Phenylendgruppen.
  Die vier Polyestercarbonate wurden auf einem S 30-Reifenhäuserextruder bei 300°C T mit 0,1 Gew.-% Kaliumperfluorbutansulfonat und 0,5 Gew.-% N-Methyltetrachlorphthalimid vermischt.
  

In the following examples, the relative solution viscosity η rel in dichloromethane was determined at 25 ° C. and a concentration of 0.5% by weight.

• I. Preparation of diphenol monoesters of carboxylic acids
  • I.1 Preparation of terephthalic acid bis- [2,2-bis (4-hydroxyphenyl) propane 7-monoester.
    
    
    2490 g of terephthalic acid, 8010 g of linear bisphenol A polycarbonate (with η rel: 1.28 and with 89 g of built-in phenol as chain terminator) and 25 g of imidazole are placed in a stirred autoclave. This mixture is heated to 220 ° C. in the course of 2 hours with stirring and in an N ₂ atmosphere. The mixture is allowed to stir at this temperature for 8 h and then heated at 250 ° C. for 4 h. During this time, 705 1 CO _{2 are released} . A vacuum of 1 torr is then applied. The glassy, brown colored product has the following key figures:
    • SZ 0.9
    • OHZ 178 found
    • OHZ 190 calculated.
  • I.2 Preparation of p-hydroxybenzoic acid [2,2-bis (4-hydroxyphenyl) propane / monoester.
    
    
    2071.8 g of p-hydroxybenzoic acid, 4005 g of a bisphenol A polycarbonate (with η rel: 1.28 and with 44.5 g of built-in phenol as chain terminator) and 15 g of imidazole are placed in a stirred autoclave. This mixture is heated to 200 ° C. in the course of 2 h with stirring and in an N ₂ atmosphere. At approx. 150 ° C, CO ₂ elimination occurs. The reaction mixture is left to stir at this temperature for a further 5 h until approximately 330 l of CO _{2 have been} eliminated and the acid number is approximately 1.5. A vacuum of 1 torr is then applied. The glassy, slightly colored, transparent product has the following key figures:
    • SZ 1
    • OHZ 298 found
    • OHZ 321 calculated.
  • I.3 Preparation of adipic acid bis [2,2-bis (4-hydroxyphenyl) propane] monoesters
    
    
    14.6 g of adipic acid, 53.4 g of bisphenol A polycarbonate (with η rel: 1.28 and with 0.59 g of built-in phenol as chain terminator) and 0.6 g of imidazole are placed in a stirred flask. This mixture is heated to 200 ° C. within 30 minutes with stirring. The elimination of CO ₂ is complete after approx. 2 h. Then 1 h a vacuum of 20 torr was applied. The glassy, brown colored product has the following key figures:
    • SZ 1
    • OHZ 190 found
    • OHZ calculated 197.6.
  • 1.4 Preparation of the bis- [2,2-bis- (4-hydroxyphenyl) propane / monoester of hydrogenated dimer fatty acid.
    53.4 g of bisphenol A polycarbonate (with t rel: 1.28 and with 0.59 g of built-in phenol as chain terminator), 56 g of hydrogenated dimer fatty acid are placed in a stirred flask M n 560 (Empol 1010 from Unilever Emery) and 0.6 g of imidazole. This mixture is heated to 200 ° C. within 30 minutes. The elimination of CO ₂ is complete after 4 h. A vacuum of 20 torr is then applied for 1 h. The brownish, resinous product has the following key figures:
    • SZ 0.5
    • OHZ 144 calculated
    • OHZ 105 found.
  • I.5 Preparation of sebacic acid bis- [2,2-bis (4-hydroxyphenyl) propane / monoesters
    
    
    20.2 g of sebacic acid, 53.4 g of bisphenol A polycarbonate (with η rel: 1.28 and with 0.59 g of built-in phenol as chain terminator) and 0.6 g of imidazole are placed in a stirred flask. This mixture is heated to 200 ° C. within 30 minutes with stirring. After about 2 hours, the C0 ₂ elimination is complete. A vacuum of 20 torr is then applied for 1 h.
    The brownish, slightly resinous product has the following key figures:
    • SZ 0.5
    • OHZ 180 calculated
    • OHZ 174 found.
  • I.6 Preparation of the bis-L2,2-bis (4-hydroxyphenyl) propane 7-monoester of a hydrogenated dimer fatty acid hexanediol polyester.
    120.2 g of a COOH-terminated, hydrogenated dimer fatty acid hexanediol polyester ( M n = 1220; OH number = 92), 53.4 g of bisphenol A polycarbonate, (with η rel: 1.28, and with 0.59 g of built-in phenol as chain terminator) and 0.6 g of imidazole. This mixture is heated to 200 ° C. within 30 minutes with stirring. After about 4 hours, the CO ₂ ablation ends. A vacuum of 20 torr is then applied. The brownish oil has the following key figures:
    • SZ 0.5
    • OHZ S2 calculated
    • OHZ 85 found.
  • 1.7 Preparation of a mixture of terephthalic acid bis [2,2-bis (4-hydroxyphenyl) propane] monoester and isophthalic acid bis [2,2-bis (4-hydroxyphenylypropane / monoester in a molar ratio of 1 :1.
    
    
    1.245 kg of terephthalic acid, 1.245 kg of isophthalic acid, 8.010 kg of bisphenol A polycarbonate (mean rel: 1.28 and with 88.9 g of built-in phenol as chain terminator) and 7.5 g of imidazole are placed in a stirred flask. This mixture is heated to 220 ° C. in the course of 2 hours with stirring and under an N2 atmosphere. From approx. 150 ° C, the CO ₂ elimination occurs slowly, which increases with increasing reaction temperature. The reaction mixture is left to stir at this temperature for a further 11 h until about 700 l of CO _{2 have been} eliminated and the acid number is 0.6. A vacuum of about 1 Torr is applied to complete the reaction and separate free phenol from the reaction mixture. 380 g of phenol are distilled off at about 1 torr within 1 h. The glassy, slightly brown colored, transparent product has the following key figures:
    • SZ 0.5
    • OHZ 186-187 found
    • OHZ 190 calculated.
  • I.8 Preparation of a mixture according to Example I.7 but in a molar ratio of 3: 1.
    1245 g of terephthalic acid, 415 g of isophthalic acid, 5340.3 g of bisphenol A polycarbonate (with η rel: 1.28 and with 59.4 g of built-in phenol as chain terminator) and 15 g of imidazole are placed in a stirred autoclave. This mixture is heated to 200 ° C. in the course of 2 h with stirring and in an N ₂ atmosphere. From approx. 150 ° C, CO ₂ elimination occurs slowly. The reaction mixture is stirred for a further 18 h at this temperature, while 470 l of CO ₂ are simultaneously split off and the acid number is 0.9 towards the end of the reaction. A vacuum of 1 torr is then applied within 1 h. The glassy, slightly brown colored, transparent and brittle product has the following key figures:
    • SZ 0.6
    • OHZ 185-187 found
    • OHZ 190 calculated.
  • I.9 Preparation of a mixture according to Example I.7, but in a molar ratio of 9: 1.
    2241 g of terephthalic acid, 249 g of isophthalic acid, 8010 g of bisphenol A polycarbonate (with η rel: 1.28 and with 89 g of incorporated phenol as chain terminator) and 25 g of imidazole are placed in a stirred autoclave. This mixture is heated to 220 ° C. in the course of 2 hours with stirring and in an N ₂ atmosphere. The reaction mixture is still at 7 h this temperature is stirred, while at the same time 702 1 C0 _{2 are} split off and the acid number is 0.8. A vacuum of 1 Torr at 250 ° C. is then applied to the glassy, brittle and later crystallizing product within 1 h. The product received has the following key figures:
    • SZ 0.7
    • OHZ 184-185 found
    • OHZ 190 calculated.
• II. Production of polyester carbonates
  • II.1 Production of a polyester polycarbonate with the following structural units
    
    
    36 l of distilled water, 1049 g of 45% sodium hydroxide solution and 61.2 g of p-tert-butylphenol are dissolved in a stirred kettle. A solution of 25.2 l of methylene chloride, 10.8 l of chlorobenzene and 4.780 kg of the mixture from Example I.7 is added. 1.612 kg of phosgene are introduced with stirring at pH 13 with stirring and a nitrogen atmosphere, while at the same time 1.5 kg of 45% sodium hydroxide solution are added dropwise to keep pH 13 constant. After that 11.26 ml of N-ethylpiperidine (1 mol%) are added and the mixture is stirred for one hour. The organic phase is separated off, successively with 2% phosphoric acid and finally with dist. Washed water until electrolyte-free. Distilling off the methylene chloride gives a chlorobenzene solution from which the polymer is isolated in an evaporation extruder at an extruder temperature of 310 ° C. The rel. Viscosity of the polyester carbonate is η rel = 1.265 (0.5 g in 100 ml CH ₂ Cl ₂ ) (mechanical properties see table below).
  • II.2 Production of a polyester carbonate from 30% by weight of aromatic polyester and 70% by weight of bisphenol A polycarbonate
    2.185 kg of bisphenol A, 72.4 g of p-tert-butylphenol, 36 l of distilled water and 2.500 kg of 45% sodium hydroxide solution are dissolved in a stirred kettle. A solution of 2.456 kg of the mixture from Example I.7, 10.8 l of chlorobenzene and 25.2 l of methylene chloride is added. Under a nitrogen atmosphere, 2.722 kg of phosgene are introduced at 20-25 ° C. into this reaction mixture at pH 13, while a total of 5.3 kg of 45% sodium hydroxide solution are added dropwise to keep pH 13 constant.
    Then 19 ml of N-ethylpiperidine (1 mol%) are added and the mixture is stirred for 1 hour. The The reaction product is worked up as in Example II.1.
    The isolated polyester polycarbonate has the following key figures:
    η rel = 1.290
    (echanical properties see table below).
  • II.3 Preparation of a polyester carbonate from 50 mol% aromatic polyester (75 mol% terephthalic acid and 25 mol% isophthalic acid) with 50 mol% bisphenol A polycarbonate
    1049 g of 45% NaOH, 61.2 g of p-tert-butylphenol and 36 l of distilled water are placed in a stirred kettle. A solution of 4.780 kg of the mixture from Example 1.8, 10.8 l of chlorobenzene and 25.2 l of methylene chloride is added. 1.612 kg of phosgene are introduced with the addition of 1.5 kg of 45% strength NaOH within 40 minutes, with stirring and under a nitrogen atmosphere. Further processing is carried out as in Example II.1. The relative viscosity of the polyester carbonate is η rel = 1.277. Mechanical properties see table below.
  • II.4 Preparation of a polyester carbonate from 30% by weight of aromatic polyester (90 mol% of terephthalic acid and 10 mol% of isophthalic acid) and 70% by weight of bisphenol A polycarbonate 2.185 kg of bisphenol A, 72.4 g of p-tert-butylphenol, 36 l of distilled water and 2.5 kg of 45% NaOH are dissolved in a stirred kettle. A solution of 2.456 kg of the mixture from Example I.9, 10.8 l of chlorobenzene and 25.2 l of methylene chloride is added. 2.722 kg of phosgene are introduced into this reaction mixture with stirring and worked up as in Examples II.1 and II.2. The insulated polyester-polycarbonate has the following key figures:
    η rel = 1.264
    Mechanical properties see table below.
  • _I I.5 Preparation of a polyester carbonate from 1 mol of p-hydroxybenzoic acid and 1 mol of bisphenol A.
    2.133 kg of 45% strength _N a-tron solution, 179.9 g of p-tert-butylphenol and 36 l of distilled water are placed in a stirred kettle. A solution of 4370 g of the p-hydroxybenzoic acid bisphenol A ester from Example I.2 dissolved in 25.2 l of methylene chloride and 10.8 g of chlorobenzene is added. 2.370 kg of phosgene at pH 14 with the addition of 5.2 kg of 45% NaOH are introduced within 30 minutes with stirring and in an N ₂ atmosphere. Then 16.5 ml of N-ethylpiperidine are added and the mixture is then stirred for a further 1 h. The organic phase is worked up as in Example II.1. The relative viscosity of the polyester carbonate is M rel = 1.31. According to DTA analysis, the product shows a freezing temperature Tg of 155 ° C.
    
    The properties of the table above were measured according to:
    • 1. Carbonate-ester ratio
    • 2. Terephthalic-isophthalic acid ratio
      • a) DIN 53455
      • b) DIN 53457
      • c) DIN 53453
      • d) DIN VST / B / 50
• _II I. In the following Table II the polyester carbonates II.2, II.3 and II.4 are compared with a conventional polyester carbonate. The conventional polyester carbonate consists of a mixture of terephthalic acid and isophthalic acid with a molar ratio of 1: 1 and bisphenol A and was prepared by the interfacial process from the acid chlorides of terephthalic acid and isophthalic acid; it has a relative solution viscosity η rel of 1.26. It was mixed with bisphenol A polycarbonate (η rel: 1.28) with phenyl end groups.
  The four polyester carbonates were mixed on an S 30 tire housing extruder at 300 ° CT with 0.1% by weight potassium perfluorobutanesulfonate and 0.5% by weight N-methyltetrachlorophthalimide.
  

Claims (10)

1. A process for the preparation of diphenol monoesters of carboxylic acids, characterized in that carboxylic acids are reacted with high molecular weight polycarbonates using catalysts at temperatures between 150 ° C and 350 ° C with elimination of C0 ₂ , the production of the diphenol monoesters per carboxylic acid group carboxylic acid used a diphenol polycarbonate equivalent is used. 2. Diphenol monoesters of carboxylic acids. 3. monocarboxylic acid (diphenol) monoester according to claim 2. 4. Dicarboxylic acid bis (diphenol) monoester according to claim 2. 5. tricarboxylic acid tris (diphenol) monoester according to claim 2. 6. tetracarboxylic acid tetra (diphenol) monoester according to claim 2. 7. Use of the diphenol monoesters of carboxylic acids of claims 2-6 for the production of polyester carbonates by the interfacial process or by the pyridine process. 8. Process for the preparation of polyester carbonates from diphenols, phosgene, optionally chain terminators in the known amounts and optionally branching agents in the known amounts by the known two-phase interface process at pH values between 9 and 14, at temperatures between 0 ° C and 80 ° C using the usual organic solvents and using the usual polycondensation catalysts, 'characterized in that the diphenols are diphenol monoesters of carboxylic acids with two phenolic OH groups, optionally in combination with diphenols HO-Z-OH free of ester groups, in which -Z- an ester-, group-free aromatic is divalent radical, optionally with the use of monocarboxylic acid (diphenol) monoesters with a phenolic OH group as chain terminators and optionally with the use of diphenol monoesters of carboxylic acids with three or more than three phenolic OH groups as branching agents, the respective ls used diphenol monoesters of carboxylic acids in the organic phase of the two-phase mixture. 9. polyester carbonates obtainable by the process of claim 8. 10. Molding compositions containing the polyester carbonates of claim 8, alkali metal salts of perfluoroalkanesulfone Acids or arylsulfonic acids in amounts of 0.05-2% by weight, based on the total weight of the molding composition, and optionally N-alkyltetrachlorophthalimides, polyhalodiphenyls, polyhalodiphenyl ethers or oligocarbonates of tetrahalobisphenol-A in amounts of 0.3-5% by weight. -%, based on the total weight of the molding compound.